CN102838240B - Method and system for recovering waste water generated in carbocisteine production - Google Patents
Method and system for recovering waste water generated in carbocisteine production Download PDFInfo
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- CN102838240B CN102838240B CN201210368568.XA CN201210368568A CN102838240B CN 102838240 B CN102838240 B CN 102838240B CN 201210368568 A CN201210368568 A CN 201210368568A CN 102838240 B CN102838240 B CN 102838240B
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Abstract
The invention discloses a method and system for recovering waste water generated in carbocisteine production. The system comprises a bipolar membrane electro-dialysis desalination system and a recovering system; the recovering system comprises an acid concentrating and recovering system, a base concentrating and recovering system and a carbocisteine concentrating and recovering system. With the adoption of the system, salts in the waste water generated in carbocisteine production can be converted into corresponding acid and base so as to be removed; the obtained acid and base can be directly used in the carbocisteine production process or be used in the carbocisteine production process after an advanced treatment; the carbocisteine in the waste water is further recovered by using a carbocisteine concentrating crystallizing system. By treating the waste water generated in the carbocisteine production by using the method, organism pollution, salt pollution and ammonia nitrogen pollution are avoided; in addition, the recovered acid and base can be reused in the carbocisteine production process to realize zero emission; by using the recovered carbocisteine, the carbocisteine yield is increased and the cost of the method provided by the invention can be further reduced.
Description
Technical field
The invention belongs to pharmaceutical chemical industry field, relate in particular to a kind of S-carboxymethylcysteine factory effluent recovery method and system.
Background technology
S-carboxymethylcysteine claims again carbocisteine (Carbocisteine), and molecular formula is C
5h
9nO
4s, white crystalline powder.S-carboxymethylcysteine is sticky phlegm conditioning agent, mainly at cell levels, affects the secretion of segmental bronchus body of gland, low viscous sialomucin secretion is increased, and the generation of full-bodied rock algae Saliva Orthana reduces, thereby the viscosity of sputum is reduced, and is easy to stripping.The thick sputum that S-carboxymethylcysteine causes for diseases such as chronic bronchitis, bronchial asthmas, the difficulty of coughing up phlegm and phlegm block tracheae etc.; Also difficulty and pneumonia complication can be used for coughing up phlegm after control operation; Also can be used for children's's non-suppurative otitis media, have the deaf effect of prevention.
S-carboxymethylcysteine factory effluent is similar with typical amino acids production method waste water, has that organic concentration is high, salts contg (as ammonium radical ion, chlorion) high and ammonia nitrogen high.For this type of waste water, there are at present the treatment processs such as physico-chemical processes, biological process, physico-chemical process, reagent consumption is large, produces secondary pollution simultaneously; Too high ammonia nitrogen and chlorion, to the restraining effect of microorganism and high COD, make biological process intractability large, weak effect.
Summary of the invention
In order to solve problems of the prior art, the present invention is directed to the feature that S-carboxymethylcysteine factory effluent contains high-content salt and high value S-carboxymethylcysteine, a kind for the treatment of effect is excellent, processing cost is low S-carboxymethylcysteine factory effluent recovery method and system are provided.
The invention provides a kind of S-carboxymethylcysteine production wastewater treatment system, comprise the bipolar membrane electrodialysis desalination system and the recovery system that are interconnected, described recovery system comprises at least one and S-carboxymethylcysteine condensing crystal system in sour system for concentrating and recycling and alkali system for concentrating and recycling.
For above-mentioned S-carboxymethylcysteine production wastewater treatment system, the present invention provides following three kinds of concrete treatment systems:
,Yan chamber, ,Jian chamber, the sour chamber three compartment bipolar membrane electrodialysis system that the bipolar membrane electrodialysis desalination system of first kind treatment system is comprised of Bipolar Membrane, anion-exchange membrane, cationic exchange membrane alternative arrangement, referred to as BP-A-C/BMED bipolar membrane electrodialysis system.Described BP-A-C/BMED bipolar membrane electrodialysis system comprise positive and negative electrode, utmost point chamber and between positive and negative electrode the anion-exchange membrane of alternative arrangement, Bipolar Membrane and cationic exchange membrane successively, between the anion-exchange membrane of alternative arrangement, Bipolar Membrane and cationic exchange membrane, alternately form successively successively He Yan chamber, ,Suan chamber, alkali chamber; Acid system for concentrating and recycling is connected with sour chamber, and described alkali system for concentrating and recycling is connected with alkali chamber, and described S-carboxymethylcysteine condensing crystal system is connected with salt chamber.
,Suan chamber, the alkali/salt chamber two compartment bipolar membrane electrodialysis system that the bipolar membrane electrodialysis desalination system of Equations of The Second Kind treatment system is comprised of Bipolar Membrane, anion-exchange membrane alternative arrangement, referred to as BP-A/BMED bipolar membrane electrodialysis system, described BP-A/BMED bipolar membrane electrodialysis system comprise positive and negative electrode, utmost point chamber and between positive and negative electrode the anion-exchange membrane of alternative arrangement and Bipolar Membrane successively, between the anion-exchange membrane of alternative arrangement and Bipolar Membrane, alternately form successively successively sour chamber and alkali/salt chamber.This type systematic also includes the separation system of separated alkali and S-carboxymethylcysteine, described sour system for concentrating and recycling is connected with sour chamber, the separation system of alkali/salt chamber, separated alkali and S-carboxymethylcysteine, S-carboxymethylcysteine condensing crystal system are connected successively, separation system, the alkali system for concentrating and recycling of alkali/salt chamber, separated alkali and S-carboxymethylcysteine are connected successively, and S-carboxymethylcysteine condensing crystal system is also directly connected with alkali/salt chamber of bipolar membrane electrodialysis desalination system.
,Jian chamber, the acid/salt chamber two compartment bipolar membrane electrodialysis system that the bipolar membrane electrodialysis desalination system of the 3rd class treatment system is comprised of Bipolar Membrane, cationic exchange membrane alternative arrangement, referred to as BP-C/BMED bipolar membrane electrodialysis system, described BP-C/BMED bipolar membrane electrodialysis system comprise positive and negative electrode, utmost point chamber and between positive and negative electrode the cationic exchange membrane of alternative arrangement and Bipolar Membrane successively, between the cationic exchange membrane of alternative arrangement and Bipolar Membrane, alternately form successively successively alkali chamber and acid/salt chamber.This type systematic also includes the separation system of separating acid and S-carboxymethylcysteine, described alkali system for concentrating and recycling is connected with alkali chamber, the separation system of acid/salt chamber, separating acid and S-carboxymethylcysteine, S-carboxymethylcysteine condensing crystal system are connected successively, separation system, the sour system for concentrating and recycling of acid/salt chamber, separating acid and S-carboxymethylcysteine are connected successively, and S-carboxymethylcysteine condensing crystal system is also directly connected with acid/salt chamber of bipolar membrane electrodialysis desalination system.
The separation system of above-mentioned separated alkali and S-carboxymethylcysteine can adopt pressure reducing film distillation device; The separation system of separating acid and S-carboxymethylcysteine can adopt diffusion dialysis device or underpressure distillation device; S-carboxymethylcysteine condensing crystal system is S-carboxymethylcysteine crystallizer.
The present invention also provides the S-carboxymethylcysteine factory effluent recovery method that adopts above-mentioned treatment system.
Adopt the S-carboxymethylcysteine factory effluent recovery method of first kind treatment system to comprise step:
1) S-carboxymethylcysteine factory effluent is pumped in ，Xiang Ji chamber, salt chamber and adds electrolytic solution; In order to save energy consumption, can in sour chamber, add acid solution as initial soln, in alkali chamber, add alkaline solution or salts solution as initial soln, the preferred concentration of the acid solution adding is 0.01～0.2mol/L, and the alkaline solution adding or the preferred concentration of salts solution are 0.01～0.2mol/L; The solute of the acid solution adding has identical negatively charged ion or anion radical with the salt of wanting to remove in S-carboxymethylcysteine factory effluent, and the alkali adding or the solute of salts solution have identical positively charged ion or positively charged ion group with the salt of wanting to remove in S-carboxymethylcysteine factory effluent.
2) between positive and negative electrode, apply galvanic current, the current density of the galvanic current applying is preferably 300～1500A/m
2, S-carboxymethylcysteine factory effluent is carried out to electrodialytic desalting, sour chamber obtains acid solution, and alkali chamber obtains alkaline solution, and salt chamber obtains the S-carboxymethylcysteine aqueous solution after desalination; Resulting acid is the acid corresponding with the negatively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or negatively charged ion, and resulting alkali is the alkali corresponding with the positively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or positively charged ion.
3) stop, after electrodialytic desalting, carrying out following recycling step, this recycling step can be referring to Fig. 4:
A, gained acid solution and alkaline solution in He Jian chamber, sour chamber are reclaimed after concentrated;
The concentration of b, detection salt chamber gained S-carboxymethylcysteine solution, when concentration is greater than preset concentration value, adopt S-carboxymethylcysteine crystallizer by the concentrated post crystallization of gained S-carboxymethylcysteine solution warp, otherwise, gained S-carboxymethylcysteine solution is returned to bipolar membrane electrodialysis desalination system, re-execute step 1)～2).
The condition of above-mentioned termination electrodialytic desalting is:
The specific conductivity of on-line monitoring salt chamber stops electrodialytic desalting when the specific conductivity of salt chamber is 1～30mS/cm.
In Bipolar Membrane, water decomposition becomes hydrogen ion and hydroxide ion, and hydrogen ion enters sour chamber, and hydroxide ion enters alkali chamber, and the hydrogen ion that in S-carboxymethylcysteine factory effluent, the negatively charged ion of salt or anion radical enter in ，Yu Suan chamber, sour chamber through anion-exchange membrane is combined into acid; The hydroxide ion that in S-carboxymethylcysteine factory effluent, the positively charged ion of salt or positively charged ion group enter in ，Yu Jian chamber, alkali chamber through cationic exchange membrane is combined into alkali; Thereby reach the object that removes the salt in S-carboxymethylcysteine factory effluent.S-carboxymethylcysteine is due to its low transport number feature, so major part is retained in salt chamber.
Adopt the S-carboxymethylcysteine factory effluent recovery method of Equations of The Second Kind treatment system to comprise step:
1) S-carboxymethylcysteine factory effluent is pumped in ，Xiang Ji chamber, alkali/salt chamber and add electrolytic solution; In order to save energy consumption, in sour chamber, add acid solution as initial soln, to add the preferred concentration of acid solution be 0.01～0.2mol/L; The solute of the acid solution adding has identical negatively charged ion or anion radical with the salt of wanting to remove in S-carboxymethylcysteine factory effluent.
2) between positive and negative electrode, apply galvanic current, the current density of the galvanic current applying is preferably 300～1500A/m
2, S-carboxymethylcysteine factory effluent is carried out to electrodialytic desalting, sour chamber obtains acid solution, and alkali/salt chamber obtains S-carboxymethylcysteine after desalination and the mixing solutions of alkali; Resulting acid is the acid corresponding with the negatively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or negatively charged ion, and resulting alkali is the alkali corresponding with the positively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or positively charged ion.
3) stop, after electrodialytic desalting, carrying out following recycling step, this recycling step can be referring to Fig. 5:
A, gained acid solution in sour chamber is reclaimed after concentrated;
B, the separated alkali/salt of employing pressure reducing film distillation method chamber gained mixing solutions obtain alkaline solution and S-carboxymethylcysteine solution, and the alkaline solution that separation is obtained reclaims after concentrated; Detect the concentration of separating obtained S-carboxymethylcysteine solution, when concentration is greater than preset concentration value, adopt S-carboxymethylcysteine crystallizer by the concentrated post crystallization of gained S-carboxymethylcysteine solution warp, otherwise, gained S-carboxymethylcysteine solution is returned to bipolar membrane electrodialysis desalination system, re-execute step 1)～2).
The condition of above-mentioned termination electrodialytic desalting is:
The specific conductivity of on-line monitoring alkali/salt stops electrodialytic desalting when the specific conductivity of alkali/salt chamber is 2～30mS/cm.
In Bipolar Membrane, water decomposition becomes hydrogen ion and hydroxide ion, hydrogen ion enters sour chamber, hydroxide ion enters alkali/salt chamber, and the hydrogen ion that in S-carboxymethylcysteine factory effluent, the negatively charged ion of salt or anion radical enter in ，Yu Suan chamber, sour chamber through anion-exchange membrane is combined into acid; In S-carboxymethylcysteine factory effluent, the positively charged ion of salt or positively charged ion group are combined into alkali with hydroxide ion in alkali/salt chamber; S-carboxymethylcysteine is due to its low transport number feature, so major part is retained in alkali/salt chamber.After electrodialysis separation starts, in alkali/salt chamber, produce alkali, form the mixing solutions of alkali, S-carboxymethylcysteine factory effluent, along with proceeding of electrodialysis separation, in alkali/salt chamber, alkali concn raises, and in S-carboxymethylcysteine factory effluent, salt concn reduces, and S-carboxymethylcysteine and the alkali of producing are retained in alkali/salt chamber.
Adopt the S-carboxymethylcysteine factory effluent recovery method of the 3rd class treatment system to comprise step:
1) S-carboxymethylcysteine factory effluent is pumped in ，Xiang Ji chamber, acid/salt chamber and add electrolytic solution; In order to save energy consumption, can in alkali chamber, add alkali or salts solution as initial soln, to add the preferred concentration of alkali or salts solution be 0.01～0.2mol/L; The alkali adding or the solute of salts solution have identical negatively charged ion or anion radical with the salt of wanting to remove in S-carboxymethylcysteine factory effluent.
2) between positive and negative electrode, apply galvanic current, the current density of the galvanic current applying is preferably 300～1500A/m
2, S-carboxymethylcysteine factory effluent is carried out to electrodialytic desalting, alkali chamber obtains alkaline solution, and acid/salt chamber obtains S-carboxymethylcysteine after desalination and sour mixing solutions; Resulting acid is the acid corresponding with the negatively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or negatively charged ion, and resulting alkali is the alkali corresponding with the positively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or positively charged ion.
3) stop, after electrodialytic desalting, carrying out following recycling step, this recycling step can be referring to Fig. 5:
A, gained alkaline solution in alkali chamber is reclaimed after concentrated;
B, employing diffusive dialysis method or the separated alkali/salt of distillation under vacuum chamber gained mixing solutions obtain alkaline solution and S-carboxymethylcysteine solution, and the alkaline solution that separation is obtained reclaims after concentrated; Detect the concentration of separating obtained S-carboxymethylcysteine solution, when concentration is greater than preset concentration value, by the concentrated post crystallization of gained S-carboxymethylcysteine solution warp, otherwise, gained S-carboxymethylcysteine solution is returned to bipolar membrane electrodialysis desalination system, re-execute step 1)～2).
The condition of above-mentioned termination electrodialytic desalting is:
The specific conductivity of on-line monitoring acid/salt, when the transformation efficiency of salt reaches 25%～90% in acid/salt, stops electrodialytic desalting.
In Bipolar Membrane, water decomposition becomes hydrogen ion and hydroxide ion, hydrogen ion enters acid/salt chamber, hydroxide ion enters alkali salt chamber, and the hydroxide ion that in S-carboxymethylcysteine factory effluent, the positively charged ion of salt or positively charged ion group enter in ，Yu Jian chamber, alkali chamber through cationic exchange membrane is combined into alkali; In S-carboxymethylcysteine factory effluent, the negatively charged ion of salt or anion radical are combined into acid with hydrogen ion in sour chamber; S-carboxymethylcysteine is due to its low transport number feature, so major part is retained in acid/salt chamber.After electrodialysis separation starts, in acid/salt chamber, produce acid, form the mixing solutions of acid, S-carboxymethylcysteine factory effluent, along with proceeding of electrodialysis separation, in acid/salt chamber, acid concentration raises, and in S-carboxymethylcysteine factory effluent, salt concn reduces, and S-carboxymethylcysteine and the acid of producing are retained in acid/salt chamber.
Step 1) and 2 in above-mentioned S-carboxymethylcysteine factory effluent recovery method) can be used as independent method and be used for removing salt contained in S-carboxymethylcysteine factory effluent.
Therefore, the invention allows for a kind of bipolar membrane electrodialysis desalting method of S-carboxymethylcysteine factory effluent, the method has adopted above-mentioned bipolar membrane electrodialysis desalination system, comprises step:
1) S-carboxymethylcysteine factory effluent is pumped in salt chamber, alkali/salt chamber or ，Xiang Ji chamber, acid/salt chamber and inject electrolyte solution;
2) between positive and negative electrode, apply galvanic current, the current density of the galvanic current applying is preferably 300～1500A/m
2, S-carboxymethylcysteine factory effluent is carried out to electrodialytic desalting.
In order to save energy consumption, acid solution is pumped into sour chamber in step 1) as initial soln, alkali or salts solution are pumped into alkali chamber as initial soln, the solute of described acid solution has identical negatively charged ion or anion radical with the salt of wanting to remove in S-carboxymethylcysteine factory effluent, and described alkali or the solute of salts solution have identical positively charged ion or positively charged ion group with the salt of wanting to remove in S-carboxymethylcysteine factory effluent.The preferred concentration of the initial acid solution of described acid, alkali chamber, initial alkaline solution, initial salts solution is 0.01～0.2mol/L.
The condition of electrodialytic desalting end step 2) be "
The specific conductivity of on-line monitoring salt chamber, acid/salt chamber or alkali/salt chamber, when the specific conductivity of the salt chamber specific conductivity that is 1～30mS/cm or alkali/salt chamber the transformation efficiency that is 2～30ms/cm or acid/salt chamber salt reaches 25%～90%, stops electrodialytic desalting.
Bipolar Membrane dissociate water under DC electric field becomes hydrogen ion and hydroxide ion, negatively charged ion in hydrogen ion and S-carboxymethylcysteine factory effluent or anion radical (for example chlorion) are combined into acid, positively charged ion in hydroxide ion and S-carboxymethylcysteine factory effluent (for example ammonium radical ion) is combined into alkali, S-carboxymethylcysteine, due to its low transport number, seldom moves under electric field action.The present invention is based on above-mentioned principle and built BP-A-C/BMED, BP-A/BMED, the BP-C/BMED bipolar membrane electrodialysis system of Bipolar Membrane and yin, yang ion-exchange membrane alternative arrangement, in the middle of Bipolar Membrane and yin, yang ion-exchange membrane, with dividing plate, separate, form corresponding compartment, i.e. work area.By above-mentioned bipolar membrane electrodialysis system, the hydrogen ion that salt in S-carboxymethylcysteine factory effluent and Bipolar Membrane dissociate and hydroxide ion are in conjunction with obtaining corresponding bronsted lowry acids and bases bronsted lowry, in the bipolar membrane electrodialysis system of above-mentioned three types, S-carboxymethylcysteine is retained in respectively in the fresh water that has removed most of salt, in the alkali and salts solution of alkali/salt chamber, in the acid and salts solution of acid/salt chamber.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, in S-carboxymethylcysteine factory effluent, contain a large amount of ammonium chloride or other salt, and residual certain density S-carboxymethylcysteine, directly discharge will bring serious Organic pollutants, salt to pollute and ammonia and nitrogen pollution to water body.Therefore, adopt the inventive method the salt major part in S-carboxymethylcysteine factory effluent can be changed into corresponding bronsted lowry acids and bases bronsted lowry, thereby eliminated salt pollution; When the contained salt ammonium salt such as be ammonium chloride, ammonium ion changes into ammoniacal liquor, can reduce ammonia and nitrogen pollution; The inventive method can reclaim the S-carboxymethylcysteine in S-carboxymethylcysteine factory effluent, can eliminate Organic pollutants.Meanwhile, the bronsted lowry acids and bases bronsted lowry of conversion can be back in the production technique or other production technique of S-carboxymethylcysteine, also can reduce the quantity discharged of S-carboxymethylcysteine factory effluent in the time of cost-saving; The S-carboxymethylcysteine reclaiming has improved S-carboxymethylcysteine productive rate.
2, treatment process of the present invention is without extra chemical substance, the mild condition of adding; And recover materials is S-carboxymethylcysteine, bronsted lowry acids and bases bronsted lowry, S-carboxymethylcysteine is the product of production process, and the S-carboxymethylcysteine of recovery can improve the product yield of unit raw material; Bronsted lowry acids and bases bronsted lowry can be back to the production process of S-carboxymethylcysteine or other products, can reduce the raw material consumption of production process unit product; The S-carboxymethylcysteine reclaiming, the value that bronsted lowry acids and bases bronsted lowry produces can partly or entirely make up wastewater treatment running cost and construction cost.
3, the inventive method easily is automated, and system floor space of the present invention is little, and the inventive method can realize zero release and few discharge of S-carboxymethylcysteine factory effluent, and development potentiality is huge.
Accompanying drawing explanation
Fig. 1 is structure and the principle of work schematic diagram of ,Yan chamber, ,Jian chamber, sour chamber three compartment bipolar membrane electrodialysis (BP-A-C/BMED) systems;
Fig. 2 is structure and the principle of work schematic diagram of ,Jian chamber, acid/salt chamber two compartment bipolar membrane electrodialysis (BP-C/BMED) systems;
Fig. 3 is structure and the principle of work schematic diagram of ,Suan chamber, alkali/salt chamber two compartment bipolar membrane electrodialysis (BP-A/BMED) systems;
Fig. 4 is that the present invention is for the structural representation of the concrete enforcement of the treatment system of S-carboxymethylcysteine factory effluent;
Fig. 5 is that the present invention is for the structural representation of the concrete enforcement of the treatment system of S-carboxymethylcysteine factory effluent;
Fig. 6 is the process flow sheet of the mixing solutions of separated S-carboxymethylcysteine and alkali;
Fig. 7 is the first process flow sheet of separated S-carboxymethylcysteine and sour mixing solutions;
Fig. 8 is the second process flow sheet of separated S-carboxymethylcysteine and sour mixing solutions.
In figure: 1-cationic exchange membrane, 2-Bipolar Membrane, 3-anion-exchange membrane.
Embodiment
Principle of work shown in Fig. 1～3 is all that to take the S-carboxymethylcysteine factory effluent of implication ammonium chloride be example.Below in conjunction with specific embodiment and with reference to figure 1～3, the present invention is described in more detail, is only the present invention is described and never limits the present invention.
The three compartment 6 unit B P-A-C/BMED bipolar membrane electrodialysis system that form with Bipolar Membrane, anion-exchange membrane, cationic exchange membrane successively alternative arrangement, referring to Fig. 1, film useful area 842cm wherein
2.In the tested S-carboxymethylcysteine factory effluent of the present embodiment, ammonium chloride and S-carboxymethylcysteine content are respectively 2mol/L and 1g/L, and specific conductivity is 171mS/cm.To salt chamber, pump into S-carboxymethylcysteine factory effluent alkali chamber and using ammonia soln that concentration is 0.05mol/L as initial soln, hydrochloric acid soln that concentration is 0.05mol/L is usingd as initial soln in sour chamber, the sodium chloride solution that utmost point chamber solution is 0.5mol/L.At crossflow velocity, be under the condition of 3cm/s, additional constant voltage 16V, adopt batch operation pattern, with ammoniacal liquor, regulate the pH of salt chamber between 2～3, when salt chamber specific conductivity drops to 1～30mS/cm, stop electrodialysis separated.
Above-mentioned batch operation pattern refers to that feed liquid is disposable and adds feed liquid water tank, circular flow subsequently until the pattern that test stops.
Ammonia concn in alkali chamber is 1.66mol/L, concentration of hydrochloric acid in acid chamber is 0.92mol/L, average unit consumption of energy is 200W.h/mol, mean current efficiency 15%, and the S-carboxymethylcysteine in S-carboxymethylcysteine factory effluent has 85% to be retained in the fresh water that removes partial oxidation ammonium.
With Bipolar Membrane and cationic exchange membrane alternative arrangement, form the BP-C/BMED bipolar membrane electrodialysis system of two compartment Unit five, referring to Fig. 2, film useful area 735cm wherein
2, block board thickness is 0.132cm.In the tested S-carboxymethylcysteine factory effluent of the present embodiment ammonium chloride and S-carboxymethylcysteine content be respectively 0.5mol/L and
1g/L。To acid/salt chamber, pump into S-carboxymethylcysteine factory effluent, ammonia soln that concentration is 0.05mol/L is usingd as initial soln in alkali chamber, the sodium chloride solution that utmost point chamber is 0.5mol/L.At crossflow velocity, be that 3cm/s, current density are 500A/m
2under condition, adopt batch operation pattern, and pH value and specific conductivity in on-line monitoring alkali chamber and acid/salt chamber.When the transformation efficiency nearly 50% of acid/salt chamber salt, stop electrodialysis separated.
Ammonia concn in alkali chamber is 0.36mol/L, and the concentration of hydrochloric acid in acid/salt chamber is 0.27mol/L, and average unit consumption of energy is 600W.h/mol, and current efficiency is 20～25%; S-carboxymethylcysteine in S-carboxymethylcysteine factory effluent has 90% to be retained in acid/salt chamber.
Embodiment 3
The bipolar membrane electrodialysis system that the present embodiment adopts is with embodiment 2.In the tested S-carboxymethylcysteine factory effluent of the present embodiment, ammonium chloride and S-carboxymethylcysteine content are respectively 2mol/L and 1g/L.To acid/salt chamber, pump into S-carboxymethylcysteine factory effluent, ammonia soln that concentration is 0.05mol/L is usingd as initial soln in alkali chamber, the sodium chloride solution that utmost point chamber is 0.5mol/L.At crossflow velocity, be that 3cm/s, current density are 500A/m
2under condition, adopt batch operation pattern, and pH value and specific conductivity in on-line monitoring alkali chamber and acid/salt chamber.When the transformation efficiency 40% of acid/salt chamber salt, stop electrodialysis separated.
Ammonia concn in alkali chamber is 0.62mol/L, and the concentration of hydrochloric acid in acid/salt chamber is 0.55mol/L, and average unit consumption of energy is 350W.h/mol, and current efficiency is 28%; S-carboxymethylcysteine in S-carboxymethylcysteine factory effluent has 90% to be retained in acid/salt chamber.
Embodiment 4
With Bipolar Membrane and anion-exchange membrane alternative arrangement, form the BP-A/BMED bipolar membrane electrodialysis system of two compartment Unit five, referring to Fig. 3, film useful area 7 * 21cm wherein
2, block board thickness is 0.132cm.In the tested S-carboxymethylcysteine factory effluent of the present embodiment, ammonium chloride and S-carboxymethylcysteine content are respectively 0.5mol/L and 1g/L.To alkali/salt chamber, pump into the S-carboxymethylcysteine factory effluent of 2L, concentration is usingd as 0.1mol/L hydrochloric acid soln is as initial soln in sour chamber, the sodium chloride solution that utmost point chamber is 0.5mol/L.At crossflow velocity, be that 3cm/s, current density are 500A/m
2under condition, adopt batch operation pattern, and pH value and specific conductivity in on-line monitoring acid chamber and alkali/salt chamber.When alkali/salt chamber specific conductivity is 8.2mS/cm, stop electrodialysis separated.
Concentration of hydrochloric acid in acid chamber is 0.41mol/L, and the ammonia concn in alkali/salt chamber is 0.31mol/L.The average unit consumption of energy of this electrodialysis process (often removing the energy that 1mol salt consumes) is 125W.h/mol, and mean current efficiency is 47%, and the S-carboxymethylcysteine in S-carboxymethylcysteine factory effluent has 69% to be retained in alkali/salt chamber.
Embodiment 5
The bipolar membrane electrodialysis system that the present embodiment adopts is with embodiment 4.In the tested S-carboxymethylcysteine factory effluent of the present embodiment, ammonium chloride and S-carboxymethylcysteine content are respectively 1mol/L and 1g/L.To alkali/salt chamber, pump into S-carboxymethylcysteine factory effluent, concentration is usingd as the initial soln of 0.1mol/L hydrochloric acid soln as sour chamber, the sodium chloride solution that utmost point chamber is 0.5mol/L in sour chamber.At crossflow velocity, be that 3cm/s, current density are 500A/m
2under condition, adopt batch operation pattern, and pH value and specific conductivity in on-line monitoring acid chamber and alkali/salt chamber.When alkali/salt chamber specific conductivity is 13.8mS/cm, stop electrodialysis separated.
Concentration of hydrochloric acid in acid chamber is 0.65mol/L, and the ammonia concn in alkali/salt chamber is 0.64mol/L, and average unit consumption of energy is 114W.h/mol, and current efficiency is 42%; S-carboxymethylcysteine in S-carboxymethylcysteine factory effluent has 92% to be retained in alkali/salt chamber.
In the present invention, injector chamber electrolyte solution is not limited only to sodium chloride solution, and the electrolyte solution that adopts other is all feasible, for example ammonium sulfate.Acid solution, alkaline solution or salts solution might not be injected in He Jian chamber in acid chamber, and it is also feasible only injecting clear water.In embodiment 1～5, be all to utilize magnetic drive pump to control crossflow velocity, but be not limited to, only using magnetic drive pump as fluid transmitting power, embodiment 1～5 bipolar membrane electrodialysis device also can adopt single-stage or Multistage continuous operator scheme.
The inventive method is not limited only to process the S-carboxymethylcysteine factory effluent of containing ammonium chloride, is equally applicable to the S-carboxymethylcysteine factory effluent that contains the salt such as sodium-chlor, sodium sulfate or ammonium sulfate.
Claims (6)
1. a bipolar membrane electrodialysis desalting method for S-carboxymethylcysteine factory effluent, is characterized in that,
Bipolar membrane electrodialysis desalination system and recovery system that employing is interconnected are carried out bipolar membrane electrodialysis desalination;
Described recovery system comprises at least one and S-carboxymethylcysteine condensing crystal system in sour system for concentrating and recycling and alkali system for concentrating and recycling;
Described bipolar membrane electrodialysis desalination system is:
1. comprise positive and negative electrode, utmost point chamber and between positive and negative electrode the cationic exchange membrane of alternative arrangement, Bipolar Membrane and anion-exchange membrane successively, between the cationic exchange membrane of alternative arrangement, Bipolar Membrane and anion-exchange membrane, alternately form successively successively He Yan chamber, ,Suan chamber, alkali chamber; Acid system for concentrating and recycling is connected with sour chamber, and alkali system for concentrating and recycling is connected with alkali chamber, and S-carboxymethylcysteine condensing crystal system is connected with salt chamber;
Or, 2. comprise positive and negative electrode, utmost point chamber and the anion-exchange membrane of alternative arrangement and Bipolar Membrane successively between positive and negative electrode, between the anion-exchange membrane of alternative arrangement and Bipolar Membrane, alternately form successively successively sour chamber and alkali/salt chamber, acid system for concentrating and recycling is connected with sour chamber, the separation system of alkali/salt chamber, separated alkali and S-carboxymethylcysteine, S-carboxymethylcysteine condensing crystal system are connected successively, separation system, the alkali system for concentrating and recycling of alkali/salt chamber, separated alkali and S-carboxymethylcysteine are connected successively, and S-carboxymethylcysteine condensing crystal system is also directly communicated with alkali/salt chamber;
Or, 3. comprise positive and negative electrode, utmost point chamber and the cationic exchange membrane of alternative arrangement and Bipolar Membrane successively between positive and negative electrode, between the cationic exchange membrane of alternative arrangement and Bipolar Membrane, alternately form successively successively alkali chamber and acid/salt chamber, alkali system for concentrating and recycling is connected with alkali chamber, the separation system of acid/salt chamber, separating acid and S-carboxymethylcysteine, S-carboxymethylcysteine condensing crystal system are connected successively, separation system, the sour system for concentrating and recycling of acid/salt chamber, separating acid and S-carboxymethylcysteine are connected successively, and S-carboxymethylcysteine condensing crystal system is also directly communicated with acid/salt chamber;
Described bipolar membrane electrodialysis desalting method comprises step:
1) S-carboxymethylcysteine factory effluent is pumped in salt chamber, alkali/salt chamber or ，Xiang Ji chamber, acid/salt chamber and inject electrolyte solution;
2) between positive and negative electrode, apply galvanic current, S-carboxymethylcysteine factory effluent is carried out to electrodialytic desalting.
2. the bipolar membrane electrodialysis desalting method of S-carboxymethylcysteine factory effluent claimed in claim 1, is characterized in that:
In step 1), acid solution is pumped into sour chamber as initial soln, alkali or salts solution are pumped into alkali chamber as initial soln, the solute of described acid solution has identical negatively charged ion or anion radical with the salt of wanting to remove in S-carboxymethylcysteine factory effluent, and described alkali or the solute of salts solution have identical positively charged ion or positively charged ion group with the salt of wanting to remove in S-carboxymethylcysteine factory effluent.
3. the bipolar membrane electrodialysis desalting method of S-carboxymethylcysteine factory effluent claimed in claim 1, is characterized in that:
In step 2) in, the specific conductivity of on-line monitoring salt chamber, alkali/salt chamber or acid/salt chamber, when the specific conductivity of the salt chamber specific conductivity that is 1～30mS/cm or alkali/salt chamber the transformation efficiency that is 2～30ms/cm or acid/salt chamber salt reaches 25%～90%, stop electrodialytic desalting.
4. a S-carboxymethylcysteine factory effluent recovery method, is characterized in that,
Bipolar membrane electrodialysis desalination system and recovery system that employing is interconnected are carried out bipolar membrane electrodialysis desalination;
Described recovery system comprises at least one and S-carboxymethylcysteine condensing crystal system in sour system for concentrating and recycling and alkali system for concentrating and recycling;
Described bipolar membrane electrodialysis desalination system is:
1. comprise positive and negative electrode, utmost point chamber and between positive and negative electrode the cationic exchange membrane of alternative arrangement, Bipolar Membrane and anion-exchange membrane successively, between the cationic exchange membrane of alternative arrangement, Bipolar Membrane and anion-exchange membrane, alternately form successively successively He Yan chamber, ,Suan chamber, alkali chamber; Acid system for concentrating and recycling is connected with sour chamber, and alkali system for concentrating and recycling is connected with alkali chamber, and S-carboxymethylcysteine condensing crystal system is connected with salt chamber;
Or, 2. comprise positive and negative electrode, utmost point chamber and the anion-exchange membrane of alternative arrangement and Bipolar Membrane successively between positive and negative electrode, between the anion-exchange membrane of alternative arrangement and Bipolar Membrane, alternately form successively successively sour chamber and alkali/salt chamber, acid system for concentrating and recycling is connected with sour chamber, the separation system of alkali/salt chamber, separated alkali and S-carboxymethylcysteine, S-carboxymethylcysteine condensing crystal system are connected successively, separation system, the alkali system for concentrating and recycling of alkali/salt chamber, separated alkali and S-carboxymethylcysteine are connected successively, and S-carboxymethylcysteine condensing crystal system is also directly communicated with alkali/salt chamber;
Or, 3. comprise positive and negative electrode, utmost point chamber and the cationic exchange membrane of alternative arrangement and Bipolar Membrane successively between positive and negative electrode, between the cationic exchange membrane of alternative arrangement and Bipolar Membrane, alternately form successively successively alkali chamber and acid/salt chamber, alkali system for concentrating and recycling is connected with alkali chamber, the separation system of acid/salt chamber, separating acid and S-carboxymethylcysteine, S-carboxymethylcysteine condensing crystal system are connected successively, separation system, the sour system for concentrating and recycling of acid/salt chamber, separating acid and S-carboxymethylcysteine are connected successively, and S-carboxymethylcysteine condensing crystal system is also directly communicated with acid/salt chamber;
Described S-carboxymethylcysteine factory effluent recovery method comprises step:
1) S-carboxymethylcysteine factory effluent is pumped in salt chamber, alkali/salt chamber or ，Xiang Ji chamber, acid/salt chamber and inject electrolyte solution;
2) between positive and negative electrode, apply galvanic current, S-carboxymethylcysteine factory effluent is carried out to electrodialytic desalting, acid chamber obtains acid solution, alkali chamber obtains alkaline solution, and salt chamber, acid/salt chamber, alkali/salt chamber obtain respectively the mixing solutions of mixing solutions, the S-carboxymethylcysteine after desalination and the alkali of the S-carboxymethylcysteine aqueous solution, the S-carboxymethylcysteine after desalination and acid after desalination; Described acid is the acid corresponding with the negatively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or negatively charged ion, and described alkali is the alkali corresponding with the positively charged ion of institute's saliferous in S-carboxymethylcysteine factory effluent or positively charged ion;
3) stop, after electrodialytic desalting, according to adopted treatment system, carrying out following recycling step:
A, gained acid solution or alkaline solution in sour chamber and/or alkali chamber are reclaimed after concentrated;
The concentration of b, detection salt chamber gained S-carboxymethylcysteine solution, when concentration is greater than preset concentration value, by the concentrated post crystallization of gained S-carboxymethylcysteine solution warp, otherwise, gained S-carboxymethylcysteine solution is returned to bipolar membrane electrodialysis desalination system, re-execute step 1) ~ 2);
C, separating acid/salt chamber or alkali/salt chamber gained mixing solutions obtain acid or alkaline solution and S-carboxymethylcysteine solution, and the acid that separation is obtained or alkaline solution reclaim after concentrated; Detect the concentration of separating obtained S-carboxymethylcysteine solution, when concentration is greater than preset concentration value, by the concentrated post crystallization of gained S-carboxymethylcysteine solution warp, otherwise, gained S-carboxymethylcysteine solution is returned to bipolar membrane electrodialysis desalination system, re-execute step 1) ~ 2).
5. S-carboxymethylcysteine factory effluent recovery method claimed in claim 4, is characterized in that:
In step 1), acid solution is pumped into sour chamber as initial soln, alkali or salts solution are pumped into alkali chamber as initial soln, the solute of described acid solution has identical negatively charged ion or anion radical with the salt of wanting to remove in S-carboxymethylcysteine factory effluent, and described alkali or the solute of salts solution have identical positively charged ion or positively charged ion group with the salt of wanting to remove in S-carboxymethylcysteine factory effluent.
6. S-carboxymethylcysteine factory effluent recovery method claimed in claim 4, is characterized in that:
Step 2), in, the specific conductivity of each work area of on-line monitoring, when the specific conductivity of the salt chamber specific conductivity that is 1～30mS/cm or alkali/salt chamber the transformation efficiency that is 2～30ms/cm or acid/salt chamber salt reaches 25%～90%, stops electrodialytic desalting.
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| CN103936214A (en) * | 2013-08-02 | 2014-07-23 | 浙江赛特膜技术有限公司 | Method for bipolar membrane electrodialysis treatment of 3-aminopyrazole-4-carboxamide hemisulfate production wastewater and recycling of sulfuric acid |
| CN103990382B (en) * | 2014-05-13 | 2020-01-07 | 浙江赛特膜技术有限公司 | Method for separating and extracting methoxyamine in distillate by using electrodialysis |
| CN104230063A (en) * | 2014-10-08 | 2014-12-24 | 上海博丹环境工程技术有限公司 | Method for treating high-concentration salt-containing waste water on irbesartan aminated section and system thereof |
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| CN104261599A (en) * | 2014-10-08 | 2015-01-07 | 上海博丹环境工程技术有限公司 | Method and system for treating high-concentration salt-containing wastewater produced from heparin sodium production |
| CN104230065A (en) * | 2014-10-08 | 2014-12-24 | 上海博丹环境工程技术有限公司 | Treating method and system of high-concentration salt waste water on photosensitizer production alkaline hydrolysis section |
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| CN105174390A (en) * | 2015-07-15 | 2015-12-23 | 浙江蓝极膜技术有限公司 | Technology for recovering sulfuric acid in wastewater of medium nitrogen coupling mother liquor by bipolar membrane electrodialysis method |
| CN106007110A (en) * | 2016-06-17 | 2016-10-12 | 浙江奇彩环境科技股份有限公司 | Low-salt wastewater recycled treatment and recycling method |
| CN107215996A (en) * | 2017-07-19 | 2017-09-29 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high concentration sodium salt waste water |
| CN110776387A (en) * | 2019-09-26 | 2020-02-11 | 四川绵竹新华化工有限责任公司 | Device for preparing salt-free compound amino acid by using cystine production waste liquid |
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